CN108559371A - A kind of aqueous self-emulsifying epoxy alkyd resin and its anticorrosive paint - Google Patents
A kind of aqueous self-emulsifying epoxy alkyd resin and its anticorrosive paint Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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Abstract
The invention discloses a kind of aqueous self-emulsifying epoxy alkyd resin and preparation method thereof and and the anticorrosive paint that is prepared with this, belong to chemical technology field.The present invention is introduced into large hydrophilic molecular segment on alkyd backbone, then will be on epoxy resin graft to alkyd resin, epoxy-modified alkyd resin is prepared by self-emulsifying, preparation method and simple process, modified resin has self-emulsifying ability, additional emulsifier and amine are not needed into salt, has storage stability good, physical property and the preferable advantage of corrosion resistance.When resin prepared by the present invention is used for steel structure protective priming paint, prepared coating does not contain volatile organic matter, more environmentally-friendly, and construction safety, the comprehensive performance of film are preferable.
Description
Technical field
A kind of aqueous environment protection phthalic resin coating of present invention design, more particularly to it is a kind of to be capable of what self-emulsifying epoxy was modified
Alkyd resin and preparation method thereof.
Background technology
Phthalic resin coating have raw material is cheap and easy to get, film adhesive is good, it is bright, plentiful, to color stuffing wettability
The advantages that good, and there is good application property, by the protection applied to various steel constructions widely.However, in recent years with
It coatings industry and application towards low stainization to develop, water alcohol acid coating is being paid more and more attention and is studying.
In the preparation method of aqueous alkide resin, mainly there are Mechanical Method, acid to be neutralized into salt and self-emulsification.Mechanical Method
By additional emulsifier, in addition high-speed stirred prepares aqueous alkide resin emulsion, the lotion which prepares is unstable, uses
It is relatively difficult, it is superseded at present.It is currently used method that acid, which neutralizes salt forming method, and salt is neutralized by carboxyl, can be notable
The water solubility of aqueous alkide resin is improved, but there are poor storage stability, the problems such as cosolvent is more, and physical property is poor.
And self-emulsification improves alkyd resin water solubility by introducing hydrophilic segment in strand, does not need or adds and is few
Cosolvent, the discharge of organic solvent is reduced, and the aqueous alkide resin emulsion prepared is applied widely, under physical property
The features such as less, drops.
Epoxy resin due to itself structure and performance characteristics, be often used to improve the hardness of alkyd resin, adhesive force,
Gloss and chemicals-resistant and salt spray resistance.CN102757551A patents utilize epoxy resin modification alkyd resin, prepare
Aqueous alkide resin adhesive force, hardness all be improved significantly, but this method preparation process is complicated, adds a large amount of hydrotropies
Agent, and cause the narrow scope of application of aqueous alkide resin, storage stability poor by the method that carboxyl is neutralized into salt etc.
Problem.
Invention content
The technical solution that purpose of the present invention is to be proposed for the problem present on, this programme provide that stability is good, object
Rationality can be with the excellent waterborne epoxy modified alkyd resin of antiseptic property.
It is a further object to provide the preparation methods of the waterborne epoxy modified alkyd resin.
It is also an object of the present invention to provide the waterborne epoxy modified alkyd resins in steel construction, especially anti-corrosion bottom
The application of paint.
To achieve the above object, the technical solution that the present invention takes is：
（1）Aqueous self-emulsifying epoxy alkyd resin
A kind of self-emulsifying epoxy modified alkyd resin, is prepared by the raw material of following mass percents：Unsaturated fatty acid 25-
35%, epoxy resin：5-15%, polyalcohol：10-20%, polyacid or acid anhydrides：8-15%, the acid anhydrides containing 3 or more carboxyls：
1-5%, large hydrophilic molecular segment：5-15%, appropriate reaction dissolvent, appropriate deionized water.
Unsaturated fatty acid of the present invention is soya-bean oil, linseed oil, tung oil, castor oil, coconut oil, cottonseed oil, tall oil
At least one of oil or safflower oil.
Epoxy resin of the present invention is by epoxychloropropane or methyl epichlorohydrin and bisphenol-A, Bisphenol F or double
Polyglycidyl ether of the epoxyalkane of epoxy resin, bisphenol-A that phenol sulfone obtains through addition, polypropylene glycol, 1,6- hexylene glycols, three
The polyglycidyl ether of the polyalcohols such as hydroxymethyl-propane, glycerine；The polycarboxylic bunchings such as adipic acid, phthalic acid, dimer acid
Water glyceride and poly epihydric alcohol amine etc..The above-mentioned bisphenol-A of above-mentioned use or Bisphenol F is more preferably selected to prepare with epoxychloropropane
Epoxy resin or adipic acid polycarboxylic acid be modified made of epoxy resin.
Polyalcohol of the present invention be glycerine, pentaerythrite, neopentyl glycol, trimethylolpropane, trimethylolethane,
Diethylene glycol, ethylene glycol, xylitol, sorbierite, hexylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, butanediol,
At least one of neopentyl glycol.
Polyacid of the present invention be M-phthalic acid, ethanedioic acid, benzoic acid, phthalic anhydride, maleic anhydride,
At least one of terephthalic acid (TPA), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride.
The acid anhydrides of 3 of the present invention or more carboxyls be trimellitic anhydride, pyromellitic dianhydride, benzophenone-3,
At least one of 3 ', 4,4 '-tetracarboxylic anhydrides, hydrogenated trimellitic anhydride, hydrogenation pyromellitic dianhydride.
Large hydrophilic molecular segment of the present invention be molecular weight be 400-1000 polyethylene glycol, polypropylene glycol or one
Polyoxyethylene mono methoxy ether at least one of of the end with hydroxyl.
Solvent of the present invention is at least one of toluene, dimethylbenzene, benzene.
（2）The preparation method of aqueous self-emulsifying epoxy alkyd resin
The preparation method of aqueous self-emulsifying epoxy alkyd resin of the present invention
The acid of unsaturated fatty acid, polyalcohol, large hydrophilic molecular segment, acid anhydrides, 3 or more carboxyls is added in a kettle
The solvent of acid anhydride and the 10-20% of the above substance total amount is warming up to 180-220 DEG C, carries out esterification 6-10 hours, is reacting
Constantly divide water in the process, measure the acid value of reactant, after acid value reaches 80-150mg KOH/g, epoxy resin is added to reaction
In object, the reaction was continued 4-6 hours, and acid value is constantly measured in reaction process, until acid value reaches<30mg KOH/g, decompression abjection
After solvent, 70-80 DEG C is cooled to, appropriate amount of deionized water is then added, prepares the self-emulsifying epoxy acid modified alcoholic of certain solid content
Resin.
（3）The waterborne epoxy modified alkyd resin of the present invention is applied to aqueous anticorrosion of steel structure priming paint
Waterborne epoxy modified alkyd resin is applied to the aqueous steel construction priming paint, and mass fraction is：
Waterborne epoxy modified alkyd resin is 30-60 parts, trbasic zinc phosphate：5-10 parts, aluminum phosphate：5-10 parts, 2-6 parts of mica, sulfuric acid
Barium：10-15 parts, auxiliary agent（Antifoaming agent, dispersant, substrate wetting agents, polyurethane thickener）It is 1-3 parts, appropriate deionized water.
A certain amount of deionized water is added in abrasive disk, then be added trbasic zinc phosphate, aluminum phosphate, mica, barium sulfate with
And dispersant, high speed grinding is carried out, until fineness of grind<Then this slurry is slowly called in waterborne epoxy modified alcohol by 25um
In acid resin, related auxiliaries is added, and deionized water is added, the viscosity of coating is adjusted by polyurethane thickener, is then reached
To after suitable viscosity, discharging packaging.
Self-emulsified aqueous epoxy modified alkyd resin preparation method and simple process prepared by the present invention, for preparing is aqueous
The advantages that resin has the function of self-emulsifying, and storage stability is good, and rate of drying is fast, hardness height, strong adhesive force and impact resistance.
The anti-corrosion primer prepared by this waterborne epoxy modified alkyd resin has storage stability good, strong adhesive force, chemicals-resistant and
The good feature of salt spray resistance, using water as solvent, have environmental protection, it is easy for construction, improve the safety of transport, construction, be suitble to
It is used for the protection of steel construction.
Specific implementation mode
For a further understanding of the present invention, the present invention is illustrated with reference to specific example：
Embodiment 1
（1）The preparation of aqueous self-emulsifying epoxy alkyd resin
300g flaxseed acid, 30g pentaerythrites, 100g ethylene glycol, 20g neopentyl glycols, molecular weight 600 are added in a kettle
Polyethylene glycol 100g, 20g benzoic acid, 80g maleic anhydrides, 30g trimellitic anhydrides and 150g dimethylbenzene, are warming up to 180-220
DEG C, it carries out esterification 6-10 hours, constantly divides water during the reaction, measure the acid value of reactant, acid value reaches 80-
After 150mg KOH/g, 80g epoxy resin E51 is added in reactant, the reaction was continued 4-6 hours, is constantly surveyed in reaction process
Acid value is measured, until acid value reaches<30mg KOH/g, depressurize prolapse solvent after, cool to 70-80 DEG C, then be added 700g go from
Sub- water prepares the self-emulsifying epoxy modified alkyd resin that solid content is 50% or so, and appearance is white emulsion, the resin prepared
Thermmal storage（50 DEG C * 15 days）It does not precipitate, it is not stratified.
This self-emulsifying epoxy modified alkyd resin is prepared into anticorrosion of steel structure priming paint：20g deionized waters are added to grinding
In disk, 5g trbasic zinc phosphates, 7g aluminum phosphates, 2g micas, 15g barium sulfate and 1g dispersants is then added, carries out high speed grinding, until
Fineness of grind<Then 25um slowly calls in this slurry in the waterborne epoxy modified alkyd resins of 50g, related auxiliaries are added,
The viscosity of coating is adjusted by polyurethane thickener, after then reaching suitable viscosity, discharging packaging.Coating specific performance is shown in
Table 1.
Embodiment 2
（1）The preparation of aqueous self-emulsifying epoxy alkyd resin
300g flaxseed acid, 30g trimethylolpropanes, 100g ethylene glycol, 20g neopentyl glycols, molecular weight are added in a kettle
For 600 poly glycol monomethyl ether 100g, 20g benzoic acid, 80g maleic anhydrides, 30g trimellitic anhydrides and 150g dimethylbenzene, rise
Temperature arrives 180-220 DEG C, carries out esterification 6-10 hours, constantly divides water during the reaction, measures the acid value of reactant, acid value
After reaching 80-150mg KOH/g, 100g epoxy resin E51 is added in reactant, the reaction was continued 4-6 hours, reaction process
In constantly measure acid value, until acid value reaches<30mg KOH/g cool to 70-80 DEG C, are then added after depressurizing prolapse solvent
750g deionized waters prepare the self-emulsifying epoxy modified alkyd resin that solid content is 45% or so, and appearance is white emulsion, is prepared
The resin thermmal storage gone out（50 DEG C * 15 days）It does not precipitate, it is not stratified.
This self-emulsifying epoxy modified alkyd resin is prepared into anticorrosion of steel structure priming paint：20g deionized waters are added to grinding
In disk, 5g trbasic zinc phosphates, 7g aluminum phosphates, 2g micas, 15g barium sulfate and 1g dispersants is then added, carries out high speed grinding, until
Fineness of grind<Then 25um slowly calls in this slurry in the waterborne epoxy modified alkyd resins of 50g, related auxiliaries are added,
The viscosity of coating is adjusted by polyurethane thickener, after then reaching suitable viscosity, discharging packaging.Coating specific performance is shown in
Table 1.
Embodiment 3
（1）The preparation of aqueous self-emulsifying epoxy alkyd resin
350g eleostearic acids, 30g trimethylolpropanes, 80g ethylene glycol, 20g neopentyl glycols, molecular weight are added in a kettle is
800 poly glycol monomethyl ether 100g, 20g benzoic acid, 70g maleic anhydrides, 25g trimellitic anhydrides and 150g dimethylbenzene, heating
To 180-220 DEG C, esterification is carried out 6-10 hours, constantly divide water during the reaction, measure the acid value of reactant, acid value reaches
To after 80-150mg KOH/g, 70g epoxy resin E51 is added in reactant, the reaction was continued 4-6 hours, in reaction process
Acid value is constantly measured, until acid value reaches<30mg KOH/g cool to 70-80 DEG C, are then added after depressurizing prolapse solvent
750g deionized waters prepare the self-emulsifying epoxy modified alkyd resin that solid content is 45% or so, and appearance is white emulsion, is prepared
The resin thermmal storage gone out（50 DEG C * 15 days）It does not precipitate, it is not stratified.
This self-emulsifying epoxy modified alkyd resin is prepared into anticorrosion of steel structure priming paint：20g deionized waters are added to grinding
In disk, 5g trbasic zinc phosphates, 7g aluminum phosphates, 2g micas, 15g barium sulfate and 1g dispersants is then added, carries out high speed grinding, until
Fineness of grind<Then 25um slowly calls in this slurry in the waterborne epoxy modified alkyd resins of 50g, related auxiliaries are added,
The viscosity of coating is adjusted by polyurethane thickener, after then reaching suitable viscosity, discharging packaging.Coating specific performance is shown in
Table 1.
Embodiment 4
（1）The preparation of aqueous self-emulsifying epoxy alkyd resin
350g eleostearic acids, 25g trimethylolpropanes, 80g ethylene glycol, 20g neopentyl glycols, molecular weight are added in a kettle is
400 polyethylene glycol 130g, 20g benzoic acid, 70g M-phthalic acids, 15g pyromellitic dianhydrides and 150g dimethylbenzene, are warming up to
It 180-220 DEG C, carries out esterification 6-10 hours, constantly divides water during the reaction, measure the acid value of reactant, acid value reaches
After 80-150mg KOH/g, 70g epoxy resin E51 is added in reactant, the reaction was continued 4-6 hours, in reaction process not
It is disconnected to measure acid value, until acid value reaches<30mg KOH/g cool to 70-80 DEG C, 700g are then added after depressurizing prolapse solvent
Deionized water prepares the self-emulsifying epoxy modified alkyd resin that solid content is 45% or so, and appearance is white emulsion, is prepared
Resin thermmal storage（50 DEG C * 15 days）It does not precipitate, it is not stratified.
This self-emulsifying epoxy modified alkyd resin is prepared into anticorrosion of steel structure priming paint：20g deionized waters are added to grinding
In disk, 5g trbasic zinc phosphates, 7g aluminum phosphates, 2g micas, 15g barium sulfate and 1g dispersants is then added, carries out high speed grinding, until
Fineness of grind<Then 25um slowly calls in this slurry in the waterborne epoxy modified alkyd resins of 50g, related auxiliaries are added,
The viscosity of coating is adjusted by polyurethane thickener, after then reaching suitable viscosity, discharging packaging.Coating specific performance is shown in
Table 1.
Table 1
Claims (10)
1. a kind of aqueous self-emulsifying epoxy alkyd resin of present invention offer and preparation method thereof and the steel construction thus prepared
Protective coating, more particularly to a kind of self-emulsifying epoxy modified alkyd resin is prepared by the raw material of following mass percents：
Unsaturated fatty acid 25-35%, epoxy resin：5-15%, polyalcohol：10-20%, polyacid or acid anhydrides：8-15%, containing 3 with
On carboxyl acid anhydrides：1-5%, large hydrophilic molecular segment：5-15%, appropriate reaction dissolvent, appropriate deionized water.
2. unsaturated fatty acid according to claim 1 be soya-bean oil, linseed oil, tung oil, castor oil, coconut oil, cottonseed oil,
At least one of tall oil or safflower oil.
3. epoxy resin according to claim 1 be by epoxychloropropane or methyl epichlorohydrin and bisphenol-A, Bisphenol F,
Or bisphenol sulphone obtain epoxy resin, bisphenol-A polyglycidyl ether of the epoxyalkane through addition, polypropylene glycol, 1,6- oneself two
The polyglycidyl ether of the polyalcohols such as alcohol, trimethylolpropane, glycerine；Adipic acid, phthalic acid, dimer acid etc. are polycarboxylic
Poly glycidyl ester and poly epihydric alcohol amine etc.；It is more preferably selected from the above-mentioned bisphenol-A of above-mentioned use or Bisphenol F and epoxychloropropane
Epoxy resin made of the epoxy resin of preparation or the polycarboxylic acid of adipic acid are modified.
4. polyalcohol according to claim 1 is glycerine, pentaerythrite, neopentyl glycol, trimethylolpropane, trihydroxy methyl
Ethane, diethylene glycol, ethylene glycol, xylitol, sorbierite, hexylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, fourth
At least one of glycol, neopentyl glycol.
5. polyacid according to claim 1 is M-phthalic acid, ethanedioic acid, benzoic acid, phthalic anhydride, maleic acid
Acid anhydride, at least one of terephthalic acid (TPA), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride.
6. the acid anhydrides of 3 according to claim 1 or more carboxyls is trimellitic anhydride, pyromellitic dianhydride, hexichol first
Ketone -3,3 ', at least one of 4,4 '-tetracarboxylic anhydrides, hydrogenated trimellitic anhydride, hydrogenation pyromellitic dianhydride.
The polyethylene glycol that it is 400-1000 that 7. large hydrophilic molecular segment according to claim 1, which is molecular weight, poly- the third two
Alcohol or one end carry at least one of the polyoxyethylene mono methoxy ether of hydroxyl.
8. solvent according to claim 1 is at least one of toluene, dimethylbenzene, benzene.
9. the preparation method according to claim 1 aqueous self-emulsifying epoxy alkyd resin is：Insatiable hunger is added in a kettle
With aliphatic acid, polyalcohol, large hydrophilic molecular segment, acid anhydrides, the acid anhydrides of 3 or more carboxyls and the above substance total amount
The solvent of 10-20% is warming up to 180-220 DEG C, carries out esterification 6-10 hours, constantly divides water during the reaction, measures anti-
After answering the acid value of object, acid value to reach 80-150mg KOH/g, epoxy resin is added in reactant, the reaction was continued 4-6 hours,
Acid value is constantly measured in reaction process, until acid value reaches<30mg KOH/g cool to 70-80 DEG C after depressurizing prolapse solvent,
Then appropriate amount of deionized water is added, prepares the self-emulsifying epoxy modified alkyd resin of certain solid content.
10. the aqueous self-emulsifying epoxy alkyd resin according to claim 1 for preparing is for steel structure protective priming paint.
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| CN112266675A (en) * | 2020-11-22 | 2021-01-26 | 湖南省金海科技有限公司 | Acrylic acid modified water-based alkyd paint and preparation method thereof |
| CN113667107A (en) * | 2021-08-24 | 2021-11-19 | 张荣金 | Preparation method of hydrolysis-resistant epoxy modified alkyd resin dispersion |
| CN113861815A (en) * | 2021-10-19 | 2021-12-31 | 山东齐鲁漆业有限公司 | Emulsifiable oily medium oil solvent type alkyd resin and preparation method thereof |
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| CN112266675A (en) * | 2020-11-22 | 2021-01-26 | 湖南省金海科技有限公司 | Acrylic acid modified water-based alkyd paint and preparation method thereof |
| CN113667107A (en) * | 2021-08-24 | 2021-11-19 | 张荣金 | Preparation method of hydrolysis-resistant epoxy modified alkyd resin dispersion |
| CN113861815A (en) * | 2021-10-19 | 2021-12-31 | 山东齐鲁漆业有限公司 | Emulsifiable oily medium oil solvent type alkyd resin and preparation method thereof |
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Application publication date: 20180921 |